CN101611660A - 具有载体材料的层间绝缘膜和使用该层间绝缘膜的多层印刷电路板 - Google Patents
具有载体材料的层间绝缘膜和使用该层间绝缘膜的多层印刷电路板 Download PDFInfo
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- CN101611660A CN101611660A CNA2008800049171A CN200880004917A CN101611660A CN 101611660 A CN101611660 A CN 101611660A CN A2008800049171 A CNA2008800049171 A CN A2008800049171A CN 200880004917 A CN200880004917 A CN 200880004917A CN 101611660 A CN101611660 A CN 101611660A
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Abstract
本发明的目的是提供具有载体材料的绝缘树脂层,其可用于薄型多层印刷电路板中,在用于多层印刷电路板中表现出足够的刚性。本发明如下实现了上述目的:提供了具有载体材料的层间绝缘膜,其包括由金属箔或树脂膜构成的载体材料和形成于所述载体材料一面的层间绝缘膜。层间绝缘膜由经树脂浸渍的基材构成;基材的厚度为8μm-20μm;当树脂在170℃和30kgf/cm2压力下固化1小时时,通过TMA方法测定的层间绝缘膜平面方向的伸长率为0.05%或更少。
Description
技术领域
[0001]本发明涉及一种具有载体材料的层间绝缘膜和具有该膜的多层印刷电路板。
背景技术
[0002]在相关领域中,多层印刷电路板通过以下工序制得:用环氧树脂浸渍玻璃布基材,将树脂半固化制备预浸料板,将一个或多个预浸料板放置在具有电路的电路板上,再在该预浸料板上放置铜箔,利用热板压机(hot-platepress)在压力下对产品进行一体化成型(integrally molding)。在此方法中,重复层叠含有玻璃布和铜箔的预浸料的步骤数次。这样,在每一步骤中,均可能会引进外来杂质。
[0003]近年来,为了解决上述问题,使用一种不含玻璃布的材料(称作涂胶脂铜箔(RCC))制造多层印刷电路板,在该材料中,绝缘树脂层直接层叠在铜箔上。上述方法能够制造出薄型多层印刷布线板,因此对RCC的需求显著增多(见,例如专利文件1)。
然而,当通过常规的加压工序层叠此类不含基材(诸如玻璃布)的材料时,树脂可能会在加热加压下进行层叠时流出。因此,难以精确地控制绝缘树脂层的厚度。此外,该材料可能很薄,不能容易地处理,且诸如材料破裂和弯曲等缺陷会导致低产率,并由此致使成本提高。另外,当在通过层叠此类绝缘树脂层制得的印刷电路板上安装另一部件时,由于缺乏基材(如玻璃布),难以维持印刷电路板的刚性,因此印刷电路板可能会出现翘曲,使部件和印刷电路板之间出现不良的连接。
专利文件1:日本公开未审查申请2000-244114。
发明内容
[0004]本发明提供了一种具有载体材料的层间绝缘膜,其包括由金属箔或树脂膜构成的载体材料和形成于载体材料一面的层间绝缘膜,其中该层间绝缘膜含有经树脂浸渍的基材;该基材的厚度为8μm-20μm;当树脂在170℃和30kgf/cm2压力下固化1小时时,通过TMA方法测定的层间绝缘膜平面方向的伸长率为0.05%或更少。
[0005]本发明具有载体材料的层间绝缘膜使用厚度为8μm-20μm的基材。因此,与仅由树脂形成的材料(RCC)相比,该膜具有改善的刚性,能够改善部件安装的可靠性。
[0006]在一个优选的实施方式中,当树脂在170℃和30kgf/cm2压力下固化1小时时,层间绝缘膜在200℃的贮存弹性模量为2MPa-20MPa。
[0007]在一个更优选的实施方式中,层间绝缘膜在200℃的贮存弹性模量为该层间绝缘膜室温时的贮存弹性模量的30%-80%。将另一部件安装到通过层叠此类绝缘树脂层制得的薄型印刷电路板上时,上述构造能够减少由部件重量导致印刷电路板的变形。而且,能够减少安装过程中260℃-300℃的高温而导致的印刷电路板变形。
[0008]根据本发明,提供了具有载体材料的层间绝缘膜,其具有优异的刚性,适用于制造薄型多层印刷电路板。
附图说明
[0009]图1示出本发明一个实施方式的具有载体材料的层间绝缘膜的剖面视图。
图2示出本发明一个实施方式的具有载体材料的层间绝缘膜的制造方法的剖面视图。
具体实施方式
[0010]下面将详细说明本发明具有载体材料的层间绝缘膜和具有该膜的多层印刷电路板。
[0011]图1是本发明一个实施方式的具有载体材料的层间绝缘膜的剖面视图。具有载体材料的层间绝缘膜100有由金属箔或树脂膜构成的载体材料110和形成于载体材料110一面的层间绝缘膜123。层间绝缘膜123含有用树脂120浸渍的基材130,该基材130的厚度为8μm-20μm。
[0012]本发明中使用的基材的实例包括玻璃纤维如玻璃织布和玻璃无纺织布;无机纤维如含有玻璃以外的无机化合物的织布和无纺织布;和有机纤维如芳香族聚酰胺、聚酰胺、芳香族聚酯、聚酯、聚酰亚胺和氟树脂。在这些基材中,考虑到加热过程中的刚性和强度,优选以玻璃织布为代表的玻璃纤维基材。
[0013]在本发明中作为金属箔或树脂膜的载体材料的实例包括金属箔(如铜和铜合金、铝和铝合金、铁和铁合金以及不锈钢)和树脂膜(如氟树脂、聚酰亚胺和聚酯(例如,聚对苯二甲酸丁二酯和聚对苯二甲酸乙二酯)。
[0014]本发明中使用的树脂的实例包括环氧树脂和苯氧树脂。使用这些树脂可改善获得的层间绝缘膜的耐热性。
[0015]环氧树脂的实例包括但不限于双酚A环氧树脂、双酚F环氧树脂、苯酚酚醛清漆环氧树脂、甲酚酚醛清漆环氧树脂、双酚A酚醛清漆环氧树脂、萘改性的环氧树脂、二环戊二烯改性的环氧树脂、芳烷基改性的环氧树脂和二氨基二苯基甲烷改性的环氧树脂。另选地,也可将此类环氧树脂的卤化产物用于改善所得的层间绝缘膜的阻燃性。
[0016]这些卤化环氧树脂例可以是例如重均分子量为10,000-30,000、溴化率为20%或以上的溴化环氧树脂。使用这些溴化苯氧树脂能够减少涂布到基材时树脂的流出,从而能够维持获得的层间绝缘膜的厚度。此外,这些溴化环氧树脂能够使层间绝缘膜具挠性并改善通过层叠层间绝缘膜而制得的多层印刷电路板的阻燃性。此类卤化环氧树脂或苯氧树脂的实例包括溴化双酚A型环氧树脂、溴化双酚F型环氧树脂和溴化苯氧树脂。其中,考虑到阻燃性,优选溴化双酚A型环氧树脂和溴化苯氧树脂。使用占树脂总量10wt%-50wt%的此类卤化环氧树脂或苯氧树脂。当含量大于10wt%时,能够减少树脂流出,使层间绝缘膜的厚度保持恒定,且能够确保在压力下层叠后层间绝缘膜的厚度。同时,当含量低于50wt%,能够容易地将树脂涂布到基材130,且能够在压力层叠过程中填充电路内的凹凸处。
[0017]为了改善层间绝缘膜的耐热性,优选使用甲酚酚醛清漆环氧树脂(cresol novolac epoxy resin)。为了减少层间绝缘膜的介质损耗因数(dielectric tangent),优选使用二环戊二烯改性的环氧树脂。
[0018]本发明中使用的环氧树脂并不限于这些,且它们可以单独使用或两种或多种组合使用。
[0019]当单独使用此类卤化环氧树脂时,固化后的交联密度很低,导致挠性过高。另外,将其溶解在溶剂中以制备树脂清漆时,树脂清漆的粘性会提高,致使其涂布到基材的可操作性变差。为了解决这些缺点,混入环氧当量为3000或以下的环氧树脂,其含量为树脂总量的10-45wt%。
[0020]在溴化环氧树脂或溴化苯氧树脂中,溴化率优选为20%或更多。当溴化率大于20%,所得的多层印刷电路板具有优异的阻燃性,使其达到V-0。当不使用溴化环氧树脂时,通过混合酚醛清漆型环氧树脂(novolac typeepoxy resin)和重均分子量为1,000-5,000的磷树脂能够提高层间绝缘膜的阻燃性。为了进一步提高阻燃性,可以在树脂中引入阻燃性无机填料。
[0021]本发明中使用的树脂可进一步包含环氧树脂固化剂。环氧树脂固化剂的实例包括但不限于胺、咪唑、酸酐和苯酚树脂。优选使用胺,因为即使少量的胺也足以将环氧树脂固化,并使其具有阻燃性。特别优选熔点为150℃或更高的胺,此类胺在室温下为固体并可溶于有机溶剂中,其在环氧树脂中的溶解性低,而在150℃或以上的高温下能够与环氧树脂迅速反应。具体实例包括双氰胺、二氨基二苯基甲烷和二氨基二苯基砜。此类胺溶解在溶剂中,且均匀地分散在环氧树脂清漆中。这些胺与环氧树脂的相容性低。当通过蒸发除去溶剂时,这些胺均匀地分散在环氧树脂清漆中,使室温至100℃温度下不进行反应。因此,能够提供贮存稳定性优异的环氧树脂清漆。
[0022]在本发明具有载体的层间绝缘膜中,当树脂在170℃和30kgf/cm2压力下固化1小时后,通过TMA方法测定的层间绝缘膜平面方向的伸长率为0.05%或更少。
[0023]在本发明一个优选的实施方式中,当层间绝缘膜中的树脂在170℃和30kgf/cm2压力下固化1小时后,层间绝缘膜在200℃的贮存弹性模量为2MPa-20MPa。当贮存弹性模量在上述范围时,因为线接合(wire bonding)中的凹陷减少,所以能够可靠地连接部件。
此外,层间绝缘膜在200℃的贮存弹性模量可保持在该层间绝缘膜室温下的贮存弹性模量的30%-80%。当保持率在上述范围时,即使是薄型印刷电路板,也能够在其上可靠地安装部件,而不会因为在部件安装过程中260℃-300℃的加热导致由部件重量造成的电路板变形。
[0024]除了上述材料,可以加入含量为树脂总量的1-45wt%的添加材料以提高弹性模量、线性膨胀系数、耐热性和阻燃性等,所述添加材料例如是熔融硅石、结晶硅石、碳酸钙、氢氧化铝、氧化铝、粘土、硫酸钡、云母、滑石、白碳黑(white carbon)、硼酸铝和E-玻璃微粉。当含量落在上述范围内时,层间绝缘树脂层的粘度是适宜的,使填充内电路(inner circuits)间空间的能力得到提高。
[0025]还可以添加其它添加剂,包括硅烷偶联剂如环氧硅烷或钛酸酯偶联剂(以提高金属箔和电路板之间的粘合性并提高耐湿性)、消泡剂(以防止出现空隙)、或液体型或微粉型阻燃剂。
[0026]择将树脂清漆涂布到基材,然后在80℃-180℃下干燥后不残留在树脂中的溶剂。此类溶剂的实例包括丙酮、甲乙酮、甲苯、二甲苯、n-己烷、甲醇、乙醇、甲基溶纤剂、乙基溶纤剂、甲氧基丙醇、环己酮和N,N-二甲基甲酰胺。
[0027]接下来,将详细说明本发明具有载体的层间绝缘膜的制造方法的一个实施方式。
[0028]如图2的剖面视图所示,可以如下方式制造具有载体材料110和层间绝缘膜123的具有载体材料的层间绝缘膜100。首先,将树脂组分以预定浓度溶解在溶剂中,以获得树脂清漆121,用树脂清漆121浸渍作为基材的玻璃织布130。然后,刮去多余的树脂,通过辊140使基材130改变方向,使其与载体材料110(如金属箔)层叠,由此使基材通过载体材料的支撑面(anchor side)得到支撑。用树脂清漆121浸渍基材130后,基材130由载体材料110支撑,这样不会对基材130造成任何压力。这样,能够提供变形较小的层间绝缘膜123。对于此类变形较小的层间绝缘膜,层叠和一体化(stackingand integration)步骤中的加热加压导致的尺寸变化会减少。然后,在80℃-180℃下的卧式烘箱(horizontal oven)中将树脂干燥,直到树脂中的挥发性组分的量为树脂总重量的1.5wt%或更少,由此制得具有载体材料的层间绝缘膜100。另选地,在80℃-180℃的立式烘箱(vertical oven)中连续干燥用树脂清漆121浸渍的玻璃织布130,然后将玻璃织布130夹在载体材料110(如金属箔)的粗糙面和PET膜之间,并可使用热辊进行热压接合(thermocompressionbonding)对其进行一体化加工。尽管可以选用上述任何工艺,但因为玻璃织布很薄且强度低,优选使用卧式烘箱的工艺,在该卧式烘箱中,仅有最小张力施加到玻璃织布上。
[0029]当具有载体材料的层间绝缘膜100中的载体材料为金属箔时,将金属箔加工,使其具有预定的布线图案,并将其层叠在电路板上,使用常规的真空压机(vacuum press)将产品加热加压以固化层间绝缘膜123中的树脂,由此容易地形成具有外层电路的多层印刷电路板。
当具有载体材料的层间绝缘膜100的载体材料为树脂膜时,先将树脂膜剥离,然后将具有载体材料的层间绝缘膜100层叠在电路板上。将此层间绝缘膜和电路板层叠,通过真空压机将产品加热加压以固化层间绝缘膜123,可由此形成多层印刷电路板。
实施例
[0030]下面将参照实施例更具体地说明本发明,但本发明不以任何方式受限于这些实施例。
[0031]实施例1
在甲乙酮(MEK)中,溶解10重量份溴化苯氧树脂(溴化率为25%,平均分子量:25000-30000)(下文中,对于混和量,术语″份″意指重量份)、10份双酚F型环氧树脂(环氧当量:175,Dainippon Ink And Chemicals,Incorporated,Epiclon 830)、20份双酚A型环氧树脂(环氧当量:190,Japan Epoxy resins Co.,Ltd.,828)、25份邻甲酚酚醛清漆型环氧树脂(环氧当量:220,Dainippon InkAnd Chemicals,Incorporated,Epiclon N-690)和30份萘型环氧树脂(环氧当量:170,Dainippon Ink And Chemicals,Incorporated,HP-4700),将混合物混和。向混合物加入5重量份作为固化剂的双氰胺、0.3重量份环氧硅烷偶联剂(Nippon Unicar Co.,Ltd.,A-187)和30份氢氧化铝(HP-350,Showa Denko K.K.)制备树脂清漆。
[0032]将由此获得的树脂清漆涂布到厚度为12μm的铜箔的粗糙面。另外,用树脂清漆浸渍厚度为15μm的玻璃织布。通过刮刀式涂布机(commacoater)在其上涂布了树脂清漆的铜箔表面(具有树脂清漆的一面)涂布具有树脂清漆的玻璃织布,在卧式烘箱中将产品连续干燥,由此使具有树脂清漆的玻璃织布的厚度为30μm,以提供干燥后厚度为30μm的具有B阶层间绝缘膜和铜箔的层间绝缘膜。在本文中,术语″B阶″意指浸渍层间绝缘膜的树脂清漆中的环氧树脂的反应率为10%-80%。
[0033]接下来,对含有玻璃布和环氧树脂的玻璃环氧双面覆铜箔层压板(基材厚度为0.1mm且铜箔厚度为35μm)进行布图以获得电路板。对电路板的铜箔表面进行黑化(blackened)处理后,将如上制备的具有铜箔的层间绝缘膜层叠在电路板两面,使层间绝缘膜与电路板接触。
[0034]将层叠产物夹在两个1.6mm不锈钢板(stainless-steel patches)之间,在升温速度3℃/min-10℃/min、压力10-30Kg/cm2、真空度-760至-730mmHg条件下,利用真空压机将其加热到150℃,然后在150℃下加压15min或以上,从而制备厚度为0.2mm的多层印刷电路板。
[0035]实施例2
如实施例1所述制造多层印刷电路板,不同的是用硅石(silica)(AdmatechsCo.,Ltd.,SO-25R)替代氢氧化铝。
[0036]实施例3
如实施例1所述制造多层印刷电路板,不同的是,使用的是10份双酚A型环氧树脂(环氧当量:190,Japan Epoxy resins Co.,Ltd.,828)、30份邻甲酚酚醛清漆型环氧树脂(环氧当量:220,Dainippon Ink And Chemicals,Incorporated,Epiclon N-690)和35份萘型环氧树脂(环氧当量:170,DainipponInk And Chemicals,Incorporated,HP-4700)。
[0037]
实施例4
如实施例1所述制造多层印刷电路板,不同的是,使用的是40份双酚A型环氧树脂(环氧当量:190,Japan Epoxy resins Co.,Ltd.,828)、10份邻甲酚酚醛清漆型环氧树脂(环氧当量:220,Dainippon Ink And Chemicals,Incorporated,Epiclon N-690)和5份萘型环氧树脂(环氧当量:170,DainipponInk And Chemicals,Incorporated,HP-4700)。
[0038]实施例5
如实施例1所述制造多层印刷电路板,不同的是,还加入了20份联苯基型环氧树脂(环氧当量:166,Nippon Kayaku Co.,Ltd.,NC-3000H)。
[0039]实施例6
如实施例1所述制造多层印刷电路板,不同的是,加入60份硼酸铝(YS-3A)作为无机填料,使用的是30重量份溴化苯氧树脂(溴化率:25%,平均分子量:25,000-30,000)(下文中,对于混和量,术语″份″意指重量份)和10份双酚F型环氧树脂(环氧当量:175,Dainippon Ink And Chemicals,Incorporated,Epiclon 830),并使用了固化剂和硬化促进剂。
[0040]
比较例1
如实施例1所述制造具有铜箔的预浸料,使用厚度为0.06mm的常规预浸料(基材厚度:0.05mm)和厚度为12μm的铜箔。如实施例1所述使用该具有铜箔的预浸料和电路板制造多层印刷电路板。
[0041]评价由此获得的层间绝缘膜的贮存弹性模量(200℃)、贮存弹性模量的保持率和平面方向的伸长率、以及负载下多层印刷电路板的变形。结果在表1示出。
表1
表1(续)
实施例5 | 实施例6 | 比较例1 | |
层间绝缘膜的贮存弹性模量(200℃) | 5MPa | 22MPa | 1MPa |
层间绝缘膜贮存弹性模量的保持率 | 20% | 70% | 10% |
层间绝缘膜在X方向上的伸长率 | - | 0.02% | 0.10% |
层间绝缘膜在Y方向上的伸长率 | - | 0.02% | 0.10% |
层间绝缘膜在平面方向上的伸长率 | - | 0.02% | 0.10% |
负载下多层印刷电路板的变形 | 0.5mm或更少 | 0.5mm或更少 | 大于0.5mm |
[0042]
测量程序
1.制备层间绝缘膜
将如上制得的具有B阶层间绝缘膜的带有铜箔的层间绝缘膜切成350mm×350mm(X方向×Y方向)的小块,然后在170℃和压力30kgf/cm2下加热1小时制得C阶层间绝缘膜。在本文中,术语″C阶″意指树脂清漆中的环氧树脂的反应率大于90%。将此具有C阶层间绝缘膜和铜箔的层间绝缘膜切成5mm×20mm(X方向×Y方向)的小块。然后,对具有铜箔的层间绝缘膜中的铜箔进行蚀刻,得到厚度为30μm的层间绝缘膜的测试件。在本文中,X方向是具有铜箔的层间绝缘膜的长度方向,Y方向是具有铜箔的层间绝缘膜的宽度方向。
[0043]
2.层间绝缘膜的贮存弹性模量
在200℃下,利用动态热分析仪(dynamic thermal analysis instrument)(TAInstruments Japan,DMA,5℃/min)测量上述″1″中制得的层间绝缘膜测试件。
[0044]
3.层间绝缘膜的贮存弹性模量的保持率
在200℃和室温(20-25℃)下利用动态热分析仪(TA Instruments Japan,DMA,5℃/min)测量上述″1″中制得的层间绝缘膜测试件。200℃下的贮存弹性模量(a)和室温下的贮存弹性模量(b)以[(a)/(b)]×100(%)计算出保持率。
[0045]
4.层间绝缘膜平面方向的伸长率
通过TMA方法测量上述″1″中制得的层间绝缘膜测试件的伸长率。具体而言,使用TA Instruments Japan制造的热分析仪,在拉伸负载10g和升温速度10℃/min的条件下测量50℃-260℃的伸长率。X方向的伸长率以[(负载后X方向的尺寸)/(负载前X方向的尺寸]×100(%)计算。以相同的方式,测定Y方向的伸长率。平面方向的伸长率以X方向和Y方向的伸长率的平均值计算。
[0046]
5.负载下多层印刷电路板的变形
在温度200℃、10g负载(恒定)、间距(inter-chuck distance)10mm和十字头速度(cross-head rate)0.5mm/min的条件下,使用5t Tensilon(Orientec Co.,Ltd.)测量上述制得的多层印刷电路板在负载下的变形。
Claims (9)
1.具有载体材料的层间绝缘膜,其包括:
由金属箔或树脂膜构成的载体材料,和
形成于所述载体材料一面的层间绝缘膜;
其中,所述层间绝缘膜由经树脂浸渍的基材构成;
所述基材的厚度为8μm-20μm;且
当所述树脂在170℃和30kgf/cm2压力下固化1小时时,通过TMA方法测定的层间绝缘膜平面方向的伸长率为0.05%或更少。
2.根据权利要求1所述的具有载体材料的层间绝缘膜,其中所述基材是玻璃织布。
3.根据权利要求2所述的具有载体材料的层间绝缘膜,其中当所述树脂在170℃和30kgf/cm2压力下固化1小时时,所述层间绝缘膜在200℃的贮存弹性模量为2MPa-20MPa。
4.根据权利要求3所述的具有载体材料的层间绝缘膜,其中所述层间绝缘膜在200℃的贮存弹性模量为该层间绝缘膜室温下的贮存弹性模量的30%-80%。
5.根据权利要求1所述的具有载体材料的层间绝缘膜,其中所述树脂包括环氧树脂。
6.根据权利要求1所述的具有载体材料的层间绝缘膜,其中所述树脂包含无机填料。
7.根据权利要求1所述的具有载体材料的层间绝缘膜,其中所述树脂处于B阶状态。
8.多层印刷电路板,其通过层叠权利要求1所述的具有载体材料的层间绝缘膜而制得,其中所述载体材料由金属箔构成。
9.多层印刷电路板,其通过层叠权利要求1所述的具有载体材料的层间绝缘膜中的层间绝缘膜和电路板而制得,其中所述载体材料由树脂膜构成。
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CN104349614B (zh) * | 2013-08-02 | 2019-05-28 | 味之素株式会社 | 多层印刷线路板及其制造方法 |
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